Thermoplastic elastomers of good dyeability and high strength and elasticity as well as impact-resistant polymer blends produced therefrom

Abstract

Thermoplastic elastomers of good dyeability and high strength and elasticity, the incorporated elastomeric particles of which have and average particle diameter of 0.05 to 5 μm. The thermoplastic elastomers are formed according to a method in which mixtures of propylene homopolymers and/or propylene copolymers, elastomeric C 4 C 12 olefin copolymers and/or terpolymers and C 8 to C 14 diacrylates, C 7 to C 16 diallyl compounds, C 9 to C 15 dimethacrylates, C 7 to C 10 divinyl compounds, C 12 to C 17 acrylate esters of polyalcohols, C 15 to C 21 methacrylate esters of polyalcohols and/or C 9 C 12 triallyl compounds are added to a melt. The thermoplastic elastomers, as well as mixtures of the thermoplastic elastomers with conventional polyolefins, are suitable for use in the vehicle industry, in the domestic appliances industry, in the construction industry and in medical technology.

What is claimed is:  
     
       1. Thermoplastic elastomers comprising products of the reaction of: 
       a) 20 to 80% by weight of propylene homopolymers and/or propylene copolymers;  
       b) 80 to 20% by weight of elastomeric C 4  to C 12  olefin copolymers and/or terpolymers;  
       c) 0.10 to 4.0% by weight, based on the total of the polymers used, of unsaturated monomers from the group consisting of C 8  to C 14  diacrylates, C 7  to C 16  diallyl compounds, C 9  to C 15  dimethacrylates, C 7  to C 10  divinyl compounds, C 12  to C 17  acrylate esters of polyalcohols, C 15  to C 21  methacrylate esters of polyalcohols and C 9  to C 12  triallyl compounds; and  
       d) 0.2 to 4.0% by weight based on the total of the polymers used, of thermally decomposing free radical-forming agents from the group consisting of acyl peroxides, alkyl peroxides, hydroperoxides, peroxycarbonates, peresters, ketone peroxides, peroxyketals and azo compounds,  
       wherein said thermoplastic elastomers include elastomeric particles having an average particle diameter of 0.05 to 5 μm, and  
       said reaction comprising reacting the propylene homopolymers and/or propylene copolymers, the elastomeric C 4  to C 12  olefin copolymers and/or terpolymers, the unsaturated monomers and the thermally decomposing free radical-forming agents in a melt.  
     
     
       2. The thermoplastic elastomers of claim  1 , wherein the propylene homopolymers and/or propylene copolymers are 
       a) largely isotactic propylene homopolymers synthesized by Ziegler-Natta catalysts or metallocene catalysts, or  
       b) copolymers of propylene and ethylene or α-olefins having 4 to 18 carbon atoms, random propylene copolymers, propylene block copolymers and/or random propylene block copolymers, or  
       c) mixture s of 50 to 98% by weight of the polymers a) and/or b) and 2 to 50% by weight of:  
       c1) non-isotactic propylene homopolymers having a melting point of 145° to 165° C., a melt viscosity of 200,000 to 2,000,000 cps at 190° C., a heat of crystallization of 4 to 10 calories/g and a 35 to 55% by weight solubility in diethylether,  
       c2) largely amorphous propylene homopolymers or propylene copolymers, which contain less than 10% by weight of crystalline propylene homopolymers or crystalline propylene copolymers, have an enthalpy of melting of less than 40 J/g and a melt index of 0.1 to 100 g/10 min at 230° C./2.16 kg, the largely amorphous polypropylene being a homopolymer of propylene and/or a copolymer of propylene of at least 80 mole percent of propylene and not more than 20 mole percent of one or more α-olefins of the formula CH 2 =CHR, in which R is a linear or branched alkyl group having 2 to 8 carbon atoms, and/or  
       c3) nonlinear, modified, propylene homopolymers and/or propylene copolymers, having melt indexes of 0.1 to 30 g/10 min at 230° C./2.16 kg and a ratio of the intrinsic viscosity of the nonlinear, modified propylene homopolymer and/or propylene copolymer to the intrinsic viscosity of linear propylene homopolymer and/or propylene copolymer having substantially the same weight average molecular weight of 0.20 to 0.99, or  
       d) mixtures of polymers a), b) and c).  
     
     
       3. The thermoplastic elastomers of claim  1 , wherein the propylene copolymers consist of a blend of: 
       a) 60 to 98% by weight of a crystalline copolymer of 85 to 99.5% by weight of propylene and 15 to 0.5% by weight of ethylene and/or an α-olefin of a formula CH 2 =CHR, in which R is a linear or branched alkyl group having 2 to 8 carbon atoms, and  
       b) 2 to 40% by weight of an elastic copolymer of 20 to 70% by weight of ethylene and 80 to 30% by weight of propylene and/or an α-olefin of a formula CH 2 =CHR, wherein R is a linear or branched alkyl group having 2 to 8 carbon atoms.  
     
     
       4. The thermoplastic elastomers of claims  1 ,  2  or  3 , wherein the elastomeric C 4  to C 12  olefin copolymers and/or terpolymers are ethylene-butene copolymers, ethylene-hexene copolymers and/or ethylene-octene copolymers. 
     
     
       5. The thermoplastic elastomers of claim  1 , wherein the unsaturated monomers comprise C 7  to C 10  divinyl compounds selected from the group consisting of divinyl aniline, m-divinylbenzene, p-divinylbenzene, divinylpropane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. 
     
     
       6. High impact-resistant polymer blends comprising: 
       a) 5 to 95% by weight of thermoplastic elastomers of claim  1  and  
       b) 95 to 5% by weight of:  
       b1) non-modified polyolefins of largely isotactic propylene homopolymers, copolymers of propylene and ethylene or α-olefins having 4 to 18 carbons atoms, random propylene copolymers, propylene block copolymers and/or random propylene block copolymers, non-isotactic propylene homopolymers, largely amorphous polypropylenes, nonlinear propylene polymers, and/or  
       b2) blends of  
       b2.1) 60 to 98% by weight of a crystalline copolymer of 85 to 99.5% by weight of propylene and 15 to 0.5% by weight of ethylene and/or an α-olefin of a formula CH 2 =CHR, wherein R is a linear or branched alkyl group having 2 to 8 carbon atoms, and  
       b2.2) 2 to 40% by weight of an elastic copolymer of 20 to 70% by weight of ethylene and 80 to 30% by weight of propylene and/or an α-olefin of a formula CH 2 =CHR, wherein R is a linear or branched alkyl group having 2 to 8 carbon atoms.  
     
     
       7. A method for the preparation of thermoplastic elastomers comprising the steps of: 
       a) providing 20 to 80% by weight of propylene homopolymers and/or propylene copolymers;  
       b) providing 80 to 20% by weight of elastomeric C 4  to C 12  olefin copolymers and/or terpolymers;  
       c) providing 0.10 to 4.0% by weight, based on the total of the polymers used, of unsaturated monomers from the group consisting of C 8  to C 14  diacrylates, C 7  to C 16  diallyl compounds, C 9  to C 15  dimethacrylates, C 7  to C 10  divinyl compounds, C 12  to C 17  acrylate esters of polyalcohols, C 15  to C 21  methacrylate esters of polyalcohols and/or C 9  to C 12  triallyl compounds;  
       d) providing thermally decomposing free radical-forming agents 0.4 to 4% by weight, based on the sum of the polymers used, of acyl peroxides, alkyl peroxides, hydroperoxides, peroxycarbonates, peresters, ketone peroxides, peroxyketals and/or azo compounds; and  
       e) reacting components a), b),c) and d) in a continuous kneader in a melt at mass temperatures of 150° to 300° C. and at residence times of 1 min to 35 min to form elastomeric particles in the thermoplastic elastomer having an average particle diameter of 0.05 to 5 μm.  
     
     
       8. The method for preparing thermoplastic elastomers of claim  7 , wherein the unsaturated monomers are added directly into the melt of the thermally decomposing free radical-forming agents, the propylene homopolymers and/or propylene copolymers, and the elastomeric C 4  to C 12  olefin copolymers and/or terpolymers. 
     
     
       9. The method for preparing thermoplastic elastomers of claim  7 , wherein the propylene homopolymers and/or propylene copolymers, the elastomeric C 4  to C 12  olefin copolymers and/or terpolymers and unsaturated monomers, and/or thermally decomposing free radical-forming agents are premixed before being reacted in the continuous kneader. 
     
     
       10. Hose connectors, air intake ducts, pipe seals and or sealing profiles comprising the thermoplastic elastomer of claim  1 . 
     
     
       11. The thermoplastic elastomers of claim  1  further comprising 0.01 to 2.5% by weight of stabilizers, 0.1 to 1% by weight of antistatic agents, 0.2 to 3% by weight of pigments, 0.05 to 1% by weight of nucleating agents, 5 to 40% by weight of fillers and/or reinforcing materials, 2 to 20% by weight of flame retardants and/or 0.01 to 1% by weight of processing aids, 
       wherein:  
       a) the propylene homopolymers and/or propylene copolymers are provided in an amount of 40 to 60% by weight,  
       b) the elastomeric C 4  to C 12  olefin copolymers and/or terpolymers are provided in an amount of 60 to 40% by weight,  
       c) the unsaturated monomers are provided in an amount of 0.2 to 1.5% by weight,  
       d) the thermally decomposing free radical-forming agents are provided in an amount of 0.2 to 1.5% by weight based on the total of the polymers used, and  
       e) the elastomeric particles have an average particle diameter of 0.1 to 1 μm.  
     
     
       12. The high impact-resistant polymer blends according to claim  6  wherein component a) is provided in an amount of 10 to 50% by weight of thermoplastic elastomers of claim  1  and component b) is provided in an amount of 90 to 50% by weight. 
     
     
       13. The method for making thermoplastic elastomers according to claim  7  further comprising the step of: 
       adding 0.01 to 2.5% by weight of stabilizer, 0.1 to 1% by weight of antistatic agents, 0.2 to 3% by weight of pigments, 0.05 to 1% by weight of nucleating agent, 5 to 40% by weight of fillers and/or reinforcing agents, 2 to 20% by weight of flame retardants and/or 0.01 to 1% by weight of processing aids,  
       wherein:  
       a) the propylene homopolymers and/or propylene copolymers are provided in an amount of 40 to 60% by weight;  
       b) the elastomeric C 4  to C 12  olefin copolymers and/or terpolymers are provided in an amount of 60 to 40% by weight;  
       c) the unsaturated monomers are provided in an amount of 0.2 to 1.5% by weight;  
       d) the thermally decomposing free radical-forming agents are provided in an amount of 0.2 to 1.5% by weight;  
       e) the reacting step is performed at mass temperatures of 185° to 245° C. and at residence times of 2.5 min to 6 min, and  
       f) the elastomeric particles have an average particle diameter of 0.1 to 1 μm.